Production of anhydrous aluminum chloride



March 29, 1932.

c. B. CLARK 1,851,273

PRODUCTION OF ANHYDROUS ALUMINUM CHLORIDE File@ March 27, 1928 ULPHUR Yli ALUM! NA ANU CARBON NVENTOR CYRIL B.cLARK,

ATTORNEY Patented; Mar, i

CYRIL i3.

e 'ooMPANm-ori NEW'YORK; NYY; AfcoRronA'rIoN ouNEw-'xonxi Y Y rnonuorroN, or ANuYDRous Lui/rinvia 'CuLomnE Appiicaummed Marcher?, 192s;y yserialv No; 265,065.

My invention relates'to the production of anhydrous aluminum chloride.

' ovves itsv valuerto its .ability to convert unsat-y urated compounds to saturated compounds, to

`r y crack hydrocarbons,-fand todesulfurize the oil, f

While thisinaterial isl at present usedincon siderable;quantities,,particularlyr in petrolep um refining,itsfuse Wouldbe muchmore ex- Atenslveif 1t couldbe producedy at 1a loWer l5 Cost. rSuchan accomplishment, furthermore,l i Wouldopen up? other Vfields of application, Which at present aredeterr'ed fromusingaluminum chlorideV because ofits present high The object of my .invention Vis" to provide an improved process which will permit: the cheap and eilijcient pro'ductionof anhydrous aluminunichloride. y ff *Y i Y AS. disclosed in myico-.pendingr` application,- Smidt/$231,795 iled'November 8,1927, an-l hydrous aluminum chloride can beprodu'eed b reactin' a charo'e com jrismY fan alum1na` bearing material and carbonaeeous material,k

Y A charge is* prepared fcomprisinga suit-i rable cfarbonaeeousV material, preferably an" `solid;materi'alzsuch as coke,'charcoal, ori the,V I y like, and" alumina-bearing material such as f" Y natural-'or artificialalumina;bauxitefthe with sulphurousfmaterial and hydrochloric acid gas under the iniluence of heat applied;

externally of the reaction chamber.

According to the presentA invention, anhyg drous aluminum chloride 'is produced byref acting'a chargefcoinprising ank alumina-bearf y p Y n dehydration of the hydrous aluminum chloe t ride resulting from petroleum 7Henning, etc-,P

5f' ing material vand carbonaceousjm'aterialyvith sulphurous material and hydrochloric acidV gas under the influence of heaty supplied Withy in they mass of these reaction materialsby x the combustione ay portiony of' the,A carboil naceous material contained iut-he charge with n a supplemental supply'ofoxygen. In the accompanying drawing I have shown diagrammatically one arrangement of'- A l Preferably jthe charge'is Well' dehydratedl Y Y prior to introduction ,inV to the furnac'epal-'eA 95 Vthough this may be accomplished in the fur;

apparatus foroarrying out my invention.

5 feed pipes 5,6, and? enters the chargecon- Referring to the drawing, reference :nul meral l designatesa reaction chamber'ofany" suitable construction provided' With'the usual rcharge inletQ and spent charge outlet-,3. Ay suitable distributingpipe lrconnectingvwith 'action Achamber-1v throughthe charge inlet 2!ur` taining chamberjfl, atthe bottom thereof forv introducing the rgaseous 'reaction materials "thereintd v`l)istributingWpip'e pis provided with ahood Sor isotherwise constructedto e Y .e K;

prei/ent cloggingfbythe charge. 'f y rIn the upperpart of thechamber l an out-f Y Chaam.; or@sCARSDALE,j NEW, Youn; AssIGNoRemo GENERAL cHEMrcAIH let pipe9 providedwhich fconnectspwith 1 'anysuitable type provided with the usual gas "Y,

spectively.V`Y n Suitable valves 16,. 17,

and adelivery pipes 5,y 6, 7, .11, and `l2 for con-fv trolling :the flow. of *I gases therethrough.

"exhaust pipe 11 .and deliverypipel2.l The; Y

deliverypipel y12 yleads toy acondenser 713 of y andr condensedproduct outlets-lllandlfrel .18, j2O, and '21"are" y rprovided respectively `in Vthefeerd,` exhaust,- t

' lu the preferredmanner of carrying out bearing material 'and the carbonaceous mate-` fori-initiating and maintaining the'V reaction being supplied by Combustion With lsupple4 naceous material in rthekcharge, r as explained more 1nfdetailherelnater. f

residual aluminum V4oxide* resultingpfrom the which `charge may be briquetted'or otherf Wise treated to provide'jit; in kasuitahle form.l

The amount 'of carbonacfeousnmaterialV pro-f :vided in Athe rvcharge' should be appreciably `rthe process of'my invention, thealumina-:f y

V'mental oxygen of a portion of `the carboin excess of the amot'inttheoretically required or-'thecombustion and aluminum chloride l production operations "described hereinafter.

ferred to hereinafter.- Y This charge is then introduced until the chamber is charged to the desired de th.

g'he supplemental oxygen or air which is to be used for supplying heat by combustion of a portion of the carbon is preferably dried,

for example by contact with sulfuric acid, and preferably preheated in any well-known manner, and is then blown into the reaction chamber through the feed pipe 6 and the distributing pipe 4. The passage of this combustion supporting material upwardly through the charge willfresult in the combustion of some of the carbon therein, mainly to CO, according to the equation: c

While it is conceivable that some CO2y and H2O may be formed, particularly in the lower zone of the charge, their existence will be butv transient, for the considerable excess of carbon in the chamber` will result in the reduction of these oxidation products to CO-i-H2 in the upper zone of the charge before they escape therefrom. The gaseous products of this operation are permitted to escape from the chamber through exhaust pipe 11, the valve 21 in pipe 12 being closed, and may be passed to the atmosphere or burned to supply heat for the air preheating operation previously noted. The blow is continued untila temperature intermediate 850 C. and 1350 C. is attained in the charge and then the air or oxygen supply is cut olf. Preferably the temperature is brought up close to the upper limit of the temperature range specified. f n

After, the termination of the oxygen or air blow, substantially dry hydrochloric acid gas is blown in through the feed pipe 7 and simultaneously therewith gaseous sulfur is blown in through the feed pipe 5, the two gaseous materials preferably then passing jointly into the reaction chamber as by means .of the common distributing pipe 4f.v The proportion of hydrochloric acid gas to the sulfur introduced preferably should be in slight excess of the amount required for their jointr action in the formation of aluminum chlor chloric acid are introduced more slowly than The blow will, moreover, effect a,

the air or oxygen in the preliminary blow in order to assure their thorough interaction with the hot charge, a rate of flow of the entering mixed gases of about 20 cu. ft. per hour per cu. ft. of charge (calculated at standard conditions of temperature and pressure) having been found satisfactory.

The reaction which takes place is probably best indicated by the theoretical equation:

This reaction proceeds 'best ybetween 850 C. and 1350 C. The reaction is somewhat endothermic in nature and the original heat furnished by the carbon combustion will be gradually absorbed. The temperature of the Vcharge should not be permitted to fall below 850 C., and preferably should be maintained appreciably above that temperature, for example at 1150o C. The gaseous products of the combined Lreaction of the sulfur and h drochloric acid, viz: AlCh, H2S, HCl, C CS2, etc., pass olf through the outlet 9 whence they are delivered by pipe 12, the valve 20 in pipe 11 being closed, to the condenser 13 where the gases are cooled and the AIQCL, collected, the H23, HC1, COYCSQ etc., passing off through the outlet `14:.

tion of carbon to alumina in the charge, and the proportion of hydrochloric acid to sulfur in the entering gases, should be regulated to provide amounts of each present inA kproportion of'carbon to alumina in the charge suiciently in excess of the amount required to satisfy the equation, to provide for the considerable amount of carbon thus utilized in the oxygen or air blow to supply heat, as well as for the amount ofv carbon diverted to side reactions. The exact proportion of'carbon most favorable for a given installation will vary, of course, with the nature of the furnace, amount of radiation, extent of preheating ofthe air, etc., but can readily be determined in practice by observing the content of unutilized carbon and undecomposedl alumina in the spe-nt charge.

When `the temperature in the furnace evi- `dences reduction below the proper point, the

introduction of sulfur and hydrochloric acid gas should be temporarily suspended and hot oxygen orair blown in to bring the temperature up again. If desired, hydrochloric acid gas may be blown through the charge prior to the recuperative oxygen or air blow yto The proportions ofy the reaction materials '9 5 introduced into the furnace, i. e., the proporf estos+ao+eosgaeiarioi:V f

'AigoeoessogJr-enoi: u y

The procedure `When these 'materialsfare 'sweep zj out'to`v` the oondensers i"any remaining f gaseous y products' of the :aluminum chloride reaction.- j p 1 In place'ofthe'sulfur the gaseous sulfurous vmaterial may be suppliedeither as carbon bi-VV sulfidev or Y as sulfur dioxide,V as vexplained v,in greaterdetai'l in my earlier 'application referred to above.

Y The reactions which take place with these materials areprobably-bestindi ated by the theoretical eql'iations'V f Y' used is`substan'tiallyv theA samer as in the case ,f 'ofsulphun Withf such valterations y1n amounts Y supplenti'e'ntal-ioxygeiny gaseous sulfur', anda f offmaterials, etci, as Willbeapparent to one] .skilldin the art. a n, f

-My"invention also contemplates the 1ntroduction oflthe'oxygenf-or air continuouslyl alongwithv the other; gaseous reactiongniaterials. ForY example,k Whenr usingsul-fur as the source of the sulfurous material, the hot rsmally excess of asubstantiallyy "dry hydrothe form of'relativelyr` pure oxygen`irather the combustion supporting gasgfyi'z'the pure oxygen, is rso regulated as torlj maintainV the temperature of the charge inter1nediate8500` C. and 1350or C; a--temperature approxi` mately lmidway between ftliesetwofpoints bei ingsuitableyand the'reaction'fis ypermitted.to* y proceed 'until' anhydrous aluminum Chloride ceases 'toevolyfey Fin apprec'i'able quantity( Y VTheexactiiieclianisrnof the chemical ie-' action which resultsin'the formation: of alu- 'minumc-hloride inthecontinuous operation is diflicu'lt t'o ascertain, butf it yis probable that the AIrea'ction indicated'bythe equation previously referred to, il'je., p

- Y"einenJfaoo'assi-Iii? is responsible i forftheV v greater rproportion of the anhydrous r{aliiniinumr` chloridev formed.

The carbonfin the chamber is roxidized ymainly to CO and such amount ofV carbonV asis `oxidized 'to C02 in theV lowerrreaction Zone is Vprobably reduced to CO by the 'excess carbon in the upper redueing'zone. This combined carbon reaction'is stronglyiexo therinic in nature and, in conjunction'with ythe preheated oxygen vor air, furnishes the heatV necessary to carry on the reaction.

Vhen the strongly preheated air or oxygen isiiitroduoed together y.'the'sulfun'the y* sulfurwillbe oxidized to SO2` in 'appreciable y quantities; fSuch conversion'ofthesulfur to,V S025 howevenpriorto its introduction` into Contact Withthe charge7 yhas no appreciable detrimental eect upon theproduction of an-V hydroustaluminum chloride, for the SO2 formed will be reduced to sulfur againby the f excessr carbon in the charge, thecombined're'-r actionlbeing"indicated'by the equation: n

r4Hence the formation/and4 subsequentA decomposition ofthe SO2 may be ignored insofaras the'amount of heat generated 1s con- .bon ofthe charge'vby the supplemental Voxygen introduced, ,the available heat generated being the Vheat of formation of the' VCO lfrom carbon oxygen. TheV quantity of sup-f: fpleinental' oxygen introduced over thatwhich j may combinelwith the S'Will of course oxi-k'v rvrdige the carbonfto CO Vas above explained, ftlierebygenerating theremainden of the heats` 'Y reouired to maintain the necssary high tem-1'.

perature for the reaction.'n A

ous 1 operation will result in substantially fthe corresponding reduction in the amountfof f cerned, 'and the' reaction may be' considered solely as an oxidation of a portion of the car?r edY ` Theuse 'of carbonbisulfideinthe continu-r i,

95 same basic"reactionstaking place in the hot chargefas in the'foase` of sulphur,Y except that,A

an additional amount ofv rcaibonjis' provided i. n by 'the carbon "bisulfideythus permitting-sa n carbon supplied. inthe charge. The introduc! j erable. quantities' of CO2, and VSO2 according to thew equation Jj This oxidatiom howevenwill not affect the major reaction detrimentally for in the'pres,

encel ofthe considerable excess lof carbon yin n the'charge'the anhydrous'aluminum chloride l y tion of this CSL# With 'the preheated 'air or oxygen will .result inthe formation of considi Will be produced vthetherthe'sulfurousma4 terial is in the form` of sulfur, sulfur dioxide, or carbon bisullide.

This' Oxidation of CS21 upon itsintroduction, 'will moreover result in the evolution of-a considerable quantitypof' heat Which will serve to aid'the attainmentf n of the thermal conditions desired in` 'the charge and in the entering gases..`

` If desired, the oxygen or air in the continuous operation may be introduced into the charge separatelyfrom the sulfurforcarbon bisulfide rather than through a common inlet,

Wherebypreliminaryoxidation ofthe sulfur f i or carbon ybisulfide will beto some extent avoided.A Y Y n n i In any event, the iinalornet result of the introduction of supplemental oxygen into the [chargewill be Vthe combustionofra portion yof the carbon of the charge toy VGOz as pre- A viouslyl explained, irrespective of the exact nature Aof the various intermediate reactions which may occur in the formation of theauhydrous chloride.

When SO2 is utilized primarily as the sulfurous material, the reactions in the charge Will be along the same lines asin the previous cases, except that proportionately larger amounts of carbon will have to be available in the charge to provide the necessary heat.l by combustion. The major reaction will be z The gaseous products from the continuous operation are all passed through delivery pipe l2 and into ther condenser 13 Where thev y AlzCle is collected.

In the continuous operation it is preferable to first blow air or oxygen'alone, through the charge until a temperature intermediate 850 C. andf'l350 C. is obtained, and then to introduce the oxygen, sulfurous material and hydrochloric acid gas simultaneously," as

. noted. In this fashion sutiicient heat is pro-- vided to initiate the reaction properly Without the wastev of any of the gaseous reaction materials in so doing.. f

It-Will be apparent from the foregoing that Ihave provided a method of producing anhydrous aluminum chloride which is easily and efficiently carried out. The raw ,materi-f als involved in the reaction are readily available and comparatively cheap in price, the n manner in which heat is provided and utilized is very efficient and involves butV little ex-` pense, anda very satisfactory product is ob-` tained. i Y I claim as my invention:

1. The process of manufacturing anhy-r drous aluminum chloride which comprises reacting alumina-bearing material, carbonaceous material, sulfurous material, and hydrochloric acid gas, said carbonaceous ma` teiial being considerably in excess of the theoretical amount required for the reaction and carrying out said reaction under the influenceof heat provided by combustion Withinthe mass of said reaction materials o` a portion of said carbonaceous material yWith supplemental oxygen.

Q. The process of manufacturing anhydrous aluminum chloride which comprises reactingV :ilumina-bearing material, carbonaceous`r material, sulfurous material, and hydrochloric acid gas,'said carbonaceous material being considerably in excess of the theoretical amount required for the reaction and carrying out sai-:l reaction under the influence of heat provided by intermittent combustion within the mass of said reaction Vmaterials of a portion of said caibonaceous material With supplemental oxygen.

3. The process ot manuiactuiinfy aiihydrous aluminum chloride which comprises re- 4acting alumina-bearing material, carbona-y ceous material, sulfurous material, and hydrochloric acid gas, said carbonaceous mate- `rial being considerably in excess of the theo- ;retical amount required for the reaction and carrying out said reaction under the influence of heat provided by continuous combustion within the mass of said reaction materials of .-a portion ot said carbonaceous material with supplemental oxygen.

4. The process of manufacturing anhydrous aluminum chloride underthe influence of heat which comprises contacting aluminaearing material, carbonaceous material, sulurous material and hydrochloric acid gas, :said alumina-bearing material, sulfurous material, and hydrochloric acid gas being substantially Vin reacting proportions to form anhydrous aluminum chloride and said carboiiaceous material being considerably in exits reacting proportion, and contacting suppiemental oxygen with the mass of :said materials in quantity sufficient to heat :saidmaterials to a temperature intermediate 850 C. and 13.50 C. by the combustion of a portion of said carbonaceous material, whereby 'anhydrous aluminum chloride is formed. I

5. The process of manufacturing anhydrous aluminum chloride which comprises reacting Valumina-bearing material, carbonaceous material, sulfurous material, and hydrochloric acid Yas, said carbonaceous material being consi crably in excess of the theoretical amount required for the reaction, carrying out said rcactionat a temperature intermediate 850 C. and 1350 C., and maintaining said temperature by combustion within the mass of said reaction materials of a portion of said carbonaceous material with supplemental oxygen. .y Y

(i.v The process of kmanufacturing anhydrous aluminum chloride which comprises reacting alumina-'bearing material, carbona ceous material, sulfurous material,v and hydrochloric acid gas, said carbonaceous material being considerably in excess of the theoretical amount required for the reaction, carrying out said reaction at a temperature intermediate 850 C. and'l350o C., and maintainingr said temperature by intermittent coinbustion Within the mass of said reaction materials of a portion of said carbonaceous material with'supplemental oxygen.

rials of a portion of said carbonaceous material with supplemental oxygen.

8. The process of manufacturing anhyfk r drousi'aluminum chloride which comprises 1` 5 preparinga charge comprising alumina-bean ing material and anamount lof carbonaceous Y material in excess'of the theoreticalo'amount required for the. reaction, blowingA oxygen into contact with said chargeto burn al portion of the carbonaceous material tliereinto heat the chargeto a poi-ntwherefanhydrous aluminum chloride will .be formed bythe in-. teraction with said hot charge of sulfurous material-'and hydrochloric a 3iclgas,r and then 15 introducing vsulfurous Vmaterial and hydro'- Q chloric acid gas simultaneously` into said charge to.r form anhydrousv aluminum chlo-v ride;v

Ipreparing i Va charge comprising 'aluminat Ybearing materialfand an amount of carbonaceous material lin excess ofthe theoretical amount required for the reaction, introducing an oxidizing combustion rsupporting material into said chargey toy obtain a temperature inJf termediate 850 C., and 1350C- by the comg bustion of afportion ofthe said carbonaceous material therein, and then introducing sullfurous material and hydrochloric acid gas simultaneouslyv into Ythe heated charge` to` formlanhydrous aluminum chloridej l0. The processof -manufacturingcanhyfch.

Vfdrous aluminumv chloride which comprises preparing a charge comprisingaluminafbearf ing material and an amount ofisolid carbon,

,blowing oxygen intocontact With said charge to obtain a temperature intermediate 850 C.

Vofthe carbon in said-charge, and passing gaseous'sulfurous material and hydrochloric acid gas simultaneously in contact 'with the .heated 'charge to form anhydrous aluminum chloride. Y

' drous aluminum chloride,Whichfcomprises preparing a charge comprising alun iina.bear-v ing material and an amount Vof-solid carbon termediate 850 C. and 1350 C. by the coinbustion of a portion ofthe carbon in said' chargefand .passing gaseous sulfurandhy- Y drochloric acid gas simultaneously in contact ,Witli'theheated charge toeform anhydrous aluminum chloride.

p n l2. The process of manufacturing anhydrous aluminum chloride VWhich comprises preparing a chargecomprising alumina-bean ing material and an amount .of carbonaceous material inl excess of the theoretical amount vrrequired' forthe` reaction, blowing hot voxy- K gen into contact y*with said charge to obtain 6.5 a'rtemperature insaidkr charge intermediate s' chloric acid'gas With they heated charge Where? 9. The processV of manufacturing anhy-y drous aluminum chloride which comprises f.

and l850 C. by the combustion of a portion l1. The processof manufacturing anhyy inexcess of the theoretical amounterequired jfor Vreaction,` blowing oxygen into contact With said charge to obtain a temperature in-y 850V,`C.Vand13 50 C. by the combustion offa i i portion of the carbonaceous material therein,"

then .reacting sulfurous material andhydro-A by anhydrous aluminum chloride is formed and vrepeating said blowing operation at interyals to maintain the temperature ofthe rreaction material-s `intermediate'850 C. and. 1350or C.' Y f t Y 13. The process of manufacturing anhy-k drous aluminum chloride under the influence*` of heat which comprises preparing a l'char,g,"e"V i i 'i i' comprising aluminafbearing material and an y f amount rof solid carbon in 'excess ofthe theol retical amountrequired for the reaction, then ouslyjin Contact with said charge insuitable c 4proportioi'is to produce anhydrous aluminumjjrv chloride and to, maintain a'temperature in .Q85

`said charge intermediate'850 C.-andl350 C. '14:'. The" process ofv manufacturingV anhyof heat which comprises preparing a charge comprising alumina-bearing material and an amount of carbonaceous material in excess ofl c theltheoretical 4amount required for reaction,

blowing oxygen into contactfwith said charge f to obtain a temperature Vintermediate 850 C.I and 135,0O C. by the combustion of a portion j of said carbonaceous material, and then pass.-

. ing `relatively lpure-oxygen, sulfurous matei'iah and hydrochloric'- acidfgasl continuously 110 contact with saidk charge in suitable prop portions rto produceA anhydrous aluminum chloride and to maintain theV temperature in Ysaid chargey intermediate 850 C. and l350 C. f

l In Witnesswliereof 1 have hereunto set 115 f hand. f Signed at thel city of NeWYorkN.1Y'.,this.

21st day of March,f1928`. f

CYRIL B. CLARK.`

80 passing relativelypure oxygem'sulfurousina-.1.. terial, and hydrochloric acidgassimultanef; n

CERTIFICATE 0F CORRECTICN.

Patent No. 1,851,273. Granted March 29, 1932, to

CYRIL B, CLARK.

lt is hereby `certified that error appears in the printed specification of the above numbered patent requiring correction as follows: Page 5, line 36, claim l0, after the word "carbon" insert the words in excess of the theoretical amount required for the reaction, and lines 50 and 104, claims 11 and 15, respectively, before the Word "reaction" insert the article the; and that the said Letters Patent should he read with these corrections therein that the same may conform to the record of the case in the Patent Office.

Signed and sealed this 17th day of May, A. D. 1932.

M. J. Moore, (Seal) Y Acting Commissioner of Patents. 

